Derivatives of 6-amino-1, 3-benzodioxan



Patented Oct. 8, 1946 UNHTED STATES PATENT OFFICE -4DERIVATIVES OFG-AMINO-LS-BENZO- DIOXAN Maine No Drawing. Application December 10,1943,

Serial No. 513,733

5 Claims.

1 This invention relates to a new series of chemical compoundscomprising organic derivatives of 6-amino-1,3-benzodioxan represented bythe following formula:

O EH2 useful as intermediates in the production of dyestuffs. Theinvention also contemplates dyestuffs produced therefrom.

More particularly, the present invention relates to N-substitutedderivatives of the aminobenzodioxan, the N-substituent being ap-aminophenyl radical represented and numbered for purposes of thepresent invention as in which X may represent a hydrogen, halogen,nitro, carboxy or sulfonic radical, the acyl radical of a carboxylicacid, or a sulfonamide group.

The instant application relates to the new organic bases per se. Azodyes, particularly icecolors, having novel color shades and unusuallight iastness may be derived therefrom. These new dyestuffs comprisethe subject matter of our copending application for United StatesLetters Patent, Serial No, 513,736, filed of even date.

Very few aromatic amino compounds have been known which produce ondiazotization and coupling with an ice-color coupling component strongblue to violet shades. It is one of the principal objects of the presentinvention to produce a new series of bases and ice-colors derivedtherefrom which will have these desirable shades. It is a further objectof the invention to produce a series of bases suitable for theproduction of other azo dyes and to develop such dyes therefrom.

In general, the principal objects of the present invention areaccomplished by condensing the amino-1,3-benzodioxan with apara-nitrohalogenobenzene and subsequently reducing the nitro group toan amino group. The resulting new compounds, after diazotization andcoupling, yield dyestuffs which have the desired properties.

Either para-nitrohalogenobenzene or a param'trohalogenobenzenecontaining a negative substituent ortho to the halogen radical may beused as a starting material. These negativesubstitul ents may beradicals such as halogen, nitro, carboXy, or sulfonic radicals, the acylradical of a carboxyiic acid or a sulfonamide group. In any case, aftercondensation and reduction the product constitutes anN-para-aminophenyl-substituted aminobenzodioxan. Therefore, as used inthe instant application, the expression a paraaminophenyl radicalincludes not only the paraaminophenyl radical, but also those2'-substituted-4-amino-phenyl groups in which the negative substituentsare present. Similarly, for the purposes of the present invention, theexpression a sulfonamide radica is used to designate not only the Hgroup, but also N-substituted-sulfonamides. In the latter case, thesulfonamide group may be one in which either or both of the hydrogensare substituted by an alkyl or aryl radical or ne in which thesubstituents form with the nitrogen a heterocyclic ring such as asulfonpiperidide, sulfonmorpholide or the like.

Those para-nitrohalogenobenzenes containing negative substituents, orthoto the halogen rad: ical, are particularly useful. When such materialsare used, condensation proceeds smoothly in aqueous media. Theinvention, however, is not necessarily so limited. Condensation may becarried out in any solvent compatible with the solubility and reactivityof the particular nitrohalogenobenzene employed. In some cases, ananhydrous solvent such as nitrobenzene or the like is required. In somecases, also, the use of a cupriferous catalyst may be of advantage.Generally, too, it is well to provide an acid binder such as a metaloxide, carbonate or the like.

Reduction of the nitro to an amino group may be carried out either byalkaline or by acidic reducing agents. The pH will determine whetherfree bases or salts will be produced. 'It'will'be apparent that twodifferent types of salts are possible. There may be acid salts of thebase. On the other hand, when an acidic substituent such as a carboxylicor sulfonic group is present on the p-aminophenyl radical, the acidicconstituent may be neutralized to form a salt. Both types of salts aswell as the free bases are useful. Each may be converted to the othersby appropriate treatment. References to the new bases in the instantspecification and claims are therefore intended to include not only thebases themselves but also both types ofsalts thereof.

Diazotization of some bases of the present invention in mineral acidsolution by nitrous acid produces, according to the conditions imposed,two diiierent products. In general, use of higher temperatures, greaterconcentration of the base in solution, higher mineral acid concentrationand excess nitrous acid generally lead to forma tion of an N-nitrosoderivativeof the diazonium salts. Lower temperature, lower acidconcentra j tions and controlled nitrous acid addition lead to formationof the diazonium chloride itself.

In general, the N-nitrosc diazotization prod-.

ucts lead to the production of difierent, duller and less desirableshades when coupled. The simple diazotized product leads to theproduction of the more valuable and faster shades.

tive or of a naphthylamine, or it may be the radical of a heterocyclicamine, such as, e. g., of an amine of the benzothiazole series or of adiamine or the diphenylene oxide or diphenylene sulfone series.

Thebases of the present invention also may be used in the preparation ofwater-soluble dyestuffs suitable for dyeing vegetable or animal fibers.

Inthis case, a great many of the customary version of the N-nitrosccolors to the more desirable shades is accomplished through hydrolysisof the former. This may be accomplished by heating the N-nitrosoderivatives in dilute solutions of some alkaline material suchas sodaash or the like. Reducing agents such as sodium sulfide, sodiumbisulfite or their equivalents may be included in the saponificationbath to destroy nitric oxides as they are liberated.

I In. their 'diazotized form, the bases 7 may 7 be coupled either withor without a substrate, to yield dyestufis or pigments of greatvaluebecause of their strength, variety of shade and fastnessproperties. In particular, however, the bases of the present inventionare important for the production of fast blue prints or dyeings' uponcellulosic materials. These are produced in general, 'cy impre natizgthe cell.losic material in alkalne baths with appropriate ice-colorcoupling components and then'printing solutions of the diazotized baseswhich have been bufiered and thickened upon such prepared cloth, or bypad dyeing the prepared cloth in buffered solutions of the dia zotizedbases or the diazo salts.

[The bases of the present invention may be also converted intodiazo-sulfonates. If the basic portion of these diazo-sulfonates is freefrom solubilizing groups, they may be blended with appropriate ice-colorcoupling components and oxidizing agents. Such blends may beincorporated into a printing paste, printed on vegetable fibers and thepigment developed by treatment with steam.

Substantially any of the ice-color coupling I components are generallyuseful for production of insoluble, developed dyes, and enable theproduction of a variety of colors from yellow to blue.

However, for the present purposes, the use of arylides of2-hydroxy-3-naphthoic acid is preferable. These produce, when coupledwith the diazotized bases of the present invention, the most desirableblue to violet shades.

However, the invention is not necessarily so limited. Among otherice-color coupling components which produce useful products may belisted byway of example such compounds as betanaphthol,8-arnino-2-naphthol, 8-acetylamino- 2-naphthol, benzoyi naphthols;pyrazolones and pyrazyl pyrazolones; 'hydroxy benzofluorenones;

hydroxy derivatives of phenyl naphthylamines such as7-hydroxy-1-naphthyl-m-hydroxyphenylamine; particularly the variousN-substituted amidessuch as arylides, of 5,6,'7,8-tetrahydro-2-hydrox'y-3-naphthoic acid, of 2-hydroxy-3-anthroic acid,- of methyl anddimethyl salicyclic acids, of hydroxy carbazole carboxylic acids, ofhydroxy-benzo carbazole carboxylic acids, of hydroxy-benzoacridonecarboxylic acids, oi 3,'7-diliydroxy-naphthalene-2,6 dicarboxylic acid,of

'- 204 parts of the phenolic or aminic coupling components may be used.--The coupling component, however, must carry at least one sulfonic groupin case the diazo component hasnone. Illustrative examples of suchcoupling components include salicyclic acid, resorcinol, m-phenylenediamine, the large number of naphthol-sulfonic acids such as e. g., Racid, G acid, the Cleves acids, J acid, gamma acid, J-acid urea and J-acid imide, I-I acid and many others. Pyrazolones such as sulfonicderivatives of 1-phenyl-3-methyl pyrazolone-5 also may be used.

If so desired, the new diazo components of the present invention alsomay be used for the production of disand poly-azo dyes in accordancewith the customary procedures. Depending upon their structure, the dyesobtained from the new bases are direct dyes, acid wool dyes or chromedyes. In each group, a great many of them have very valuable dyeing andfastness properties.

The invention will-be more fully illustrated in conjunction with thefollowing examples which are meant to be illustrative only and not byway of limitation. All parts are by weight unless otherwise noted.

Example 1 63 parts of 2-chloro-5-nitrobenzene sulfondiethylamide arerefluxed for 24 hours with 27.9 parts of 6-amino-1,3-benzodioxan in 200parts of water containing 11 parts of calcium carbonate. On cooling, theprecipitated material is separated by-filtration and the residueextracted with hot alcohol. Upon cooling the alcohol extract, yellowcrystals of N-(2-sulfondiethylamide-4' ni tro-phen'yl)-6-amino-1,3-benzodioxan, melting at -l21 C. are obtained. Onrecrystallizing from alcohol, the product melts at 124125 C.

Example 2 nitro compound of Example 1 are reduced at reflux temperaturein a solution containing36 parts of sodium sulfide dissolved in amixture of 120 parts of alcohol and 50 parts of Water. After-3 hours,the yellowish reaction mixture is poured on'ice and the whiteprecipitated material is collected by filtration. The productN-(2-sulfondiethylamide 4'- amino-phenyl) -6- amino-1,3-benzodioxanmelts at 10l.5-102.5 C. and has the following structure:

, 1, part "of the amine produced in Example 2 is treated with-asolutionof"1'.6'5 parts of 31.5%

hydrochloric acid in 13.65 parts of Water at a temperature of 20 C. andthen diazotized by the addition of 0.19 parts of sodium nitrite in 5parts of water. After stirring for minutes,

looted by filtration. 2.95 parts of this dried sodium diazo sulfonateare intimately mixed with 1.58 parts of the anilide of2-hyd-roxy-3-naphthoic acid. 2.5 parts of this dry color mix are 60parts of water is added and stirring is con- 5 dissolved in 26.5 partsof water containing 0.5 tinued until solution of the diazonium chloridepart of sodium chromate and 70 parts of suitable is complete. Thissolution is then buffered with carbohydrate thickener are added. lhecolor 20% sodium acetate solution to a basic test on paste is printed onboiled-out cotton cloth, the Congo red paper and then diluted to 190parts printed stripe dried and the color developed by with Water. Theresultant solution is employed l0 steaming. The print is rinsed, treatedin 2%- at room temperature to pad dye cotton cloth, soda ash solution at60 C., and finally soaped previously impregnated with an alkalinesolution at the boil. The pattern is dyed a violet shade. of the anilideof 2-hydroxy-3-naphthoic acid. Example The dyed sample is rinsed in adilute soda ash 1 31 t 35 Q, treated in a boiling 2% soda A number ofother amides were substituted for ash bath and finally soaped atelevated temperature. The cloth is dyed an even violet of good strength.

Example 4 the sulfondiethylamide of Example 2 and the procedures ofExamples 4 and 5 are repeated. New color formulations are obtainedhaving unusual color value and good general properties.

0 Illustrative results are set forth in the following- 754 parts of theamine as produced in Example table:

Melting Melting Ar rde of} Substituted point point 3 C M i d sullonamidenitro amino y o yemg compound compound naphthoic acid C'. Amide 199-200194-195 Anilide Blue-red shade. Morpholide 181-182 182-183 --.do..Strongviolet. Diethanolamide... 156-157 Oil do Deep purple. Anilide 17-178 141-142 '..d0 .Do. 0 Anisidide 151-152 158-160 a-naphthylamida.Violet purple.

2 are dissolved in parts of acetone and this Example 7 solution israpidly added to a solution of 60 parts of zinc chloride dissolved in 60parts of water at a temperature of 30 C. At this point, 1.52 parts ofsodium nitrite dissolved in 10 parts of water are slowly added. Theprecipitated ma terial is filtered, the residue is extracted twice withwarm Water, the extracts are combined with the first filtrate and thezinc chloride double salt of the diazonium chloride is separated bysaturating the solution with salt. Three parts of this dried zincchloride double salt are intimately mixed with 1.2 parts of magnesiumsulfate dihydrate. 2.5 parts of this salt mix are dissolved in 26.5parts of water containing 0.5 part of sodium acetate and 0.5 part of 50%acetic acid solution. Seventy parts of a carbohydrate thickener areadded and the color paste is printed on cotton cloth previouslyimpregnated in an alkaline bath containing the alpha-naphthylamide of2-hydroxy-3-naphthoic acid. The printed fabric is dried, rinsed in adilute soda ash bath at 66 C. and soaped at the boil. The pattern isprinted a strong violet to purple shade.

Example 5 11.3 parts of the amine produced as in Example 2 are treatedin a solution of 32.6 parts of 17% hydrochloric acid and 30 parts ofwater with 2.1 parts of sodium nitrite dissolved in 50 parts of Water.Some solid material is filtered oil, the residue being Washed withwater. The filtrate is carefully neutralized with sodium carbonate untilthe solution is just basic to Congo red test paper after which sodiumchloride is added and the precipitated, yellow diazonium chloridecollected by filtration. Four parts of the dried diazoniurn chloride aredissolved in 250 parts of water and 2 parts of neutral sodium sulfite in16 parts of water are added. To the clear solution is added sodiumchloride and the sodium diazo sulfonate whichiprecipitatesz is'col 25parts of 2 chloro-5-nitrobenzophenone are condensed at refluxtemperature with 15 parts of 6-aminol,3benzodi0xan in a mixture of partsof Water and 20 parts of alcohol in the presence of 5.5 parts of calciumcarbonate. The reaction mixture is then cooled, the reaction productsettled out and the supernatant liquid decanted. After extraction withdilute hydrochloric acid and alcohol, a yellow, crystalline residue ofN-(2-benZoyl-4=-nitrcphenyl)-6-aminol,3-benzodioxan is obtained which onrecrystallization from alcohol melts at l i2-143 0.

Example 8 '7 parts of the nitro compound of Example '7 is slowly addedto a boiling mixture of 10 parts of aqueous sodium sulfhydrate (30%) and20 parts of alcohol. When reduction is complete, 100 parts of water areadded and the precipitated material removed by filtration. On slurryin'gWith dilute hydrochloric acid, the free base is converted to ahydrochloride which is collected by filtration. When the hydrochlorideis neutralized, the free base is obtained. It melts at l63-164 C. andhas the following formula:

HzN

H2 OCGHb Example 9 0.3 part of the amine as prepared in Example 3 arestirred in 10 parts of water, treated with 1.1 parts of 5 normalhydrochloric acid and diazotized by addition of 0.084 part of sodiumnitrite dissolved in 5 parts of water. On completion of diazotization,parts of water are added and the solutionis clarified.- 25 parts of thediazo solution so obtained'aretreatedkwith 10% sodium acetate solutionto a negative acid test against Congo red paper and then with sodiumbicarbonate solution to a neutral test to litmus paper. Water is addedto a total of 100 parts and cotton cloth, previously impregnated inalkaline solution of the anilide of 2-hydroxy-3-naphthoic acid, ispadded in this bath. The resulting dyeing is rinsed, heated at the boilin 5% soda ash solution and soaped at elevated temperature. A deeppurple dyeing results.

Example To 580 parts of water are added 110 parts of sodium2-chloro-5-nitrobenzene sulfonate (95%), 55 parts of calcium carbonateand 58.0 parts of 6-amino-l,3-benzodioxan. Under a nitrogen atmospherethe reaction mixture is stirred at reflux temperature for 24 hours andthen 48.0 parts of potassium carbonate are added. After filtration atthe elevated temperature, 83 parts of potassium chloride are strewn inportionwise and th temperature is lowered to C. The light orangeprecipitate of the potassium salt of N-(2- sulfo 4'- nitro phenyl) 6amino 1,3- benzodioxan is filtered ofi and washed with ice water on thefilter to remove residual potassium chloride.

NH XE:

Example 11 35.0 parts of the salt obtained in Example 10 are slurried in81 parts of water at 50 C. While agitating efficiently, 81 parts ofsodium sulfhydrate solution (38% aqueous solution) are run in duringone-half hour. After heating the resultant clear red solution for about4 hour at 50 C., and three hours at 65 C., the solution is treated with30.0 parts of potassium chloride. The temperature of the resultingslurry is lowered to 5 C. and the precipitated product separated byfiltration and washed on the filter with a little cold 20% potassiumchloride. The residue is slurried in 250 parts of water and hydrochloricacid (1.19) is added until the solution shows an acid reaction to Congored paper. After stirring for hour, soda ash is added until the solutionis basic to brilliant yellow paper, charcoal is added and theundissolved material is filtered oif. Acidification of the filtrate,with hydrochloric acid, produces a white precipitate which is filteredoil, washed with ice water and dried at 45 C. Th product, N -(2'-sulfo-4'-amino phenyl) 6 amino 1,3- benzodioxan, is a white solidreadily soluble in alkaline solution.

Example 12 1.6 parts of N-(2'-sulfo-e'-amino-phenyl -6-amino-1,3-benzodioxan produced according to Example 11 is stirred in 35parts of water and dis- 8 solved by the addition of a solution of 0.2part of sodium hydroxid in 5 parts of water. The hydrochloride isprecipitated in finely divided form by running in 2.46 parts of 37%hydrochloric acid. After lowering the temperature of the slurry to 5 C.,diazotization is accomplished by adding slowly 0.35 part of sodiumnitrite dissolved in 5 parts of water. An apple-green slurry results.3.2 parts of 5,5-dihydroxy-2,2- dinaphthylamine-7,7-disulfonic acid(41.7%) are dissolved in 40 parts of water containing 2.7 parts ofsodium carbonate, the temperature of the solution is adjusted to about 5C. and the diazo slurry poured in while agitating efficiently. Couplingis complete within one-half hour, yielding a deep blue solution. Thetemperature is then raised to C. and 30.0 parts of sodium chlorideadded. After lowering the temperature to 20 C., the precipitateddyestuii is collected onthe filter and is dried at 55 C. The dark powderresulting readily dissolved in water yielding a deep blue solution ofreddish shade.

Example 13 0.5 part of the dyestuff as obtained in Example 12 isdissolved in 500 parts of water. 50 parts of this solution are dilutedwith 250 parts of water and then 3.5 parts of 10% Glaubers salt and 1.0part of 10% sulfuric acid are added. Five parts of woolen flannel arewell boiled out in 1% soap solution, rinsed in fresh water and enteredinto this dye bath. The temperature is raised to the boil and maintainedthus for one hour while th woolen piece goods is well agitated. Afterremoval from the dye bath, the wool is rinsed in hot water, scaped at 65C., rinsed again and finally dried. It is levelly dyed a royal blue ofdistinctive brightness.

Example 14 50.0 parts of the standard dye solution prepared in Example13 are diluted with parts of water and 15 parts of 10% sodium chloridesolution are added. The temperature of this dy bath is adjusted at 50 C.and 5 parts of bleached cotton piece goods previously wet out in 1% soapsolution is entered and is eificiently agitated. The temperature israised to the boil, maintained thus for one hour and the cotton piecgoods is removed. It is rinsed, treated at 65 C. in 1% soap solution,again rinsed and dried. An extremely bright blue dyeing of markedgreenish shade resulted.

Example 15 Dyestuffs of distinctive colors valuable because ofbrightness and general fastness properties are obtained by diazotizationof the bases of the present invention and coupling of the resultingdiazo compounds with a variety of coupling components. The followinglist illustrates some of the dyestuffs obtainable and the shadesproduced from their application:

, Direct cotton Dyestufis Color of dye Acid v 001 dyeing dyeingN-(2'-sulfo-4-amino- 2-hydroxy naphthalene- Purple Corinthphenyl)-6-emino-1,3- 3,6-disulfonic acid. benzodioxanN-(2-su1fo-4-amlno- 2-amino-5-hydroxy-naph- Red-blue Maroon phcnyl)-6amino-1,3- thalenefl-sulfonic acid. benzodioxan N-(2'-sulfo-4-amino-5,5-dihydroxy-2,2-d Royalblue.-. Navyblue Navyblue.

phenyl)-6-amino-l,3- naphthy1urea-7,7-d1- benzodioxan sullonic acid.N-(2-sulio-4-amino- 1-(4-sulfophenyl)-3- Brown-red Red phenyl)-0-ammo-1,3- methylpyrazolone-fi. benzodioxan Direct cotton DyestuffsColor of dye Acid wool dyeing dyeing N-(2 -su1f 0-4 -amino- Il-amino-S-hydroxy-naph- Purple Black phenyl)-6-amino-1,3-tha1ene-3,6-disulfonic benzodioxan (acid) acid H aniline (alkaline). N-2-sulfo-4-amino- Z-hydroxy benzoic acid. Light brown" Khaki (topchromed) p enyl) -6-an1ino-1,3- benzodioxan N- (2-sulio-4-amino- Acetoacetanilide Orange Golden orange phenyl) -6-amino-l ,3- benzodioxan N(2-sulio-4 -amino- 1 1,3-dihydroxy benzene Brown Golden brownphenyl)-6-amino-1,3- benzodioxan (neutral) II sulianilic acid(alkaline). N-(2 -suliondietl1yl- 2-hydroxy naphthalene- Violet Purpleamide-4-aminophenyl)- 3,6-disulfonic acid. 6-amino-1,3-benzodioxan N-(2-sulIonamide-4 5,5-dihydr0xy-2, 2-di- Corinth Purple.

aminophenyl)- 6 naphthylurea-7,7-diamino-1,3-benzodioxan sulfonic acid.N-(2-benzoyl-4-amino- 5,5'dihydroxy-2,2-di- Red-blue Navy blue.

pheny1)-6-arnino-1,3- naphthylamine-7,7- benzodioxan disulfonic acid.N-(2-sulfo-4-aminol-naphthylamine phenyl) -6-amino-1,3- benzodioxan(diazotized) l-naphthylamine-7-su1- ionic acid (diazotized) BlackGreen-blue. N-phenyl-N-fi-hydroxy- 2-naphthylamine-7- sulionio acid.

We claim: 3. A chemical compound according to claim 1 1. Chemicalcompounds selected from the group in which X represents a mononuclearpara-airlinophenyl radical, and the salts of said compounds.

2. A chemical compound according to claim 1 in which X represents a2'-substituted-4'-aminophenyl radical, the 2'-substituent being asulfonic radical.

in which X represents a 2-substituted-4-aminophenyl radical, the2'-substituent being a sulfonamide radical.

4. A chemical compound according to claim 1 in which X represents a2-substituted-4'-aminophenyl radical, the 2'-substituent beingsulfonmorpholide.

5. A chemical compound according to claim 1 in which X represents a2'-substituted-4'-aminophenyl radical, the 2'-substituent being thebenzoyl radical.

HANS Z. LECHER. JOHN P. GOULDING. ROBERT P. PARKER.

